Monoazo dyes containing sulfoindole coupling components

ABSTRACT

Monoazo dyes of the formula ##STR1## wherein R 1  is hydrogen, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, halogen, C 2  -C 4  alkanoylamino or is an unsubstituted or substituted arylsulfonyl, aryloxy or arylcarbonyl radical; R 2  is hydrogen, halogen, an unsubstituted or substituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula ##STR2## R 3  is an unsubstituted or substituted alkyl or aryl radical; R 4  is hydrogen or alkyl; and R 5  and R 6  are each independently hydrogen or an unsubstituted or substituted alkyl, cycloalkyl or aryl radical, with the proviso that R 1  may not be hydrogen or halogen if R 2  is an unsubstituted or substituted aryloxysulfonyl radical, a radical of the formula ##STR3## or the trifluoromethyl group, and the sulfo group is attached to the benzene ring of the indole radical, produce dyeings of good light- and wetfastness properties on polyamide material. In particular, the dyeings obtained have shade constancy when subjected to increases in temperature.

The present invention has for its object to provide novel monoazo dyeswhich are suitable for dyeing natural and synthetic polyamides from anaqueous bath, which furthermore dye said materials in shades in therange from yellow to orange and, in addition to having good fastnessproperties such as lightfastness, wetfastness and resistance toformaldehyde, in particular do not give rise to thermochromism. It hasnow been found that the monoazo dyes of the formula (1) below meet theserequirements.

Accordingly, the invention relates to monoazo dyes of the formula##STR4## wherein R₁ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen,C₂ -C₄ alkanoylamino or is an unsubstituted or substituted arylsulfonyl,aryloxy or arylcarbonyl radical; R₂ is hydrogen, halogen, anunsubstituted or substituted alkyl, aryloxy or aryloxy oraryloxysulfonyl radical or a radical of the formula ##STR5## R₃ is anunsubstituted or substituted alkyl or aryl radical; R₄ is hydrogen oralkyl; and R₅ and R₆ are each independently hydrogen or an unsubstitutedor substituted alkyl, cycloalkyl or aryl radical, with the proviso thatR₁ may not be hydrogen or halogen if R₂ is an unsubstituted orsubstituted aryloxysulfonyl radical, a radical of the formula ##STR6##or the trifluoromethyl group, and the sulfo group is attached to thebenzene ring of the indole radical.

R₁ as C₁ -C₄ alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, isobutyl or tert-butyl.

R₁ as C₁ -C₄ alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,sec-butoxy, isobutoxy or tert-butoxy.

R₁ as C₂ -C₄ alkanoylamino is e.g. acetylamino, propionylamino orbutyrylamino.

Where R₁ is an unsubstituted or substituted arylsulfonyl, aryloxy orarylcarbonyl radical, the aryl moiety is preferably a radical of thebenzene or naphthalene series which may be further substituted, forexample by C₁ -C₄ alkyl groups such as methyl and ethyl, C₁ -C₄ alkoxygroups such as methoxy and ethoxy, halogen such as fluorine, chlorineand bromine, and C₁ -C₆ alkanoylamino groups such as acetylamino, andhydroxyl.

R₁ and/or R₂ as halogen may be fluorine, chlorine or bromine.

Where R₂ is an unsubstituted or substituted aryloxy or aryloxysulfonylradical, the aryl moiety is a radical of the benzene or naphthaleneseries which may be further substituted, for example by C₁ -C₄ alkylgroups such as methyl and ethyl, C₁ -C₄ alkoxy groups such as methoxyand ethoxy, halogen such as fluorine, chlorine and bromine, C₁ -C₆alkanoylamino groups such as acetylamino, and hydroxyl.

Unsubstituted or substituted alkyl radicals R₂, R₃, R₅ or R₆ arepreferably each independently a straight chain or branched C₁ -C₁₂alkyl, preferably C₁ -C₄ alkyl, radical which may be furthersubstituted, for example by halogen such as fluorine, chlorine orbromine, hydroxyl, cyano, C₁ -C₄ alkoxy such as methoxy or ethoxy, andC₁ -C₆ alkanoyl groups such as the acetyl or propionyl group, and thebenzoyl group. The alkyl radical R₃ can also be substituted by sulfo.Typical examples of alkyl radicals R₂, R₃, R₅ and R₆ are: methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl andtrifluoromethyl.

Unsubstituted or substituted aryl radicals R₃, R₅ and R₆ are preferablyeach independently a radical of the benzene or naphthalene series whichcan be further substituted, for example by C₁ -C₄ alkyl groups such asmethyl, C₁ -C₄ alkoxy groups such as methoxy and ethoxy, halogen such asfluorine, chlorine or bromine, trifluoromethyl, C₁ -C₆ alkanoylaminogroups such as acetylamino, and hydroxyl and carboxyl. The aryl radicalR₃ can also be substituted by sulfo. In particular, an aryl radical R₃,R₅ and R₆ is a phenyl radical which can be substituted by methyl,trifluoromethyl and chlorine.

An alkyl radical R₄ is preferably a straight chain or branched C₁ -C₁₂alkyl and, most preferably, a C₁ -C₈ alkyl radical. Typical examples ofsuch alkyl radicals are: methyl, ethyl, propyl, isopropyl, butyl,sec-butyl, tert-butyl, isobutyl, pent-1-yl, pent-3-yl, hept-1-yl,hept-3-yl and oct-1-yl.

R₅ and R₆ as unsubstituted or substituted cycloalkyl may each preferablybe independently a cycloalkyl group containing 5- to 7-membered ringswhich may be further substituted, for example by C₁ -C₄ alkyl such asmethyl. The cyclohexyl group is preferred.

Preferred monoazo dyes of the formula (1) are those wherein R₁ ishydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, C₂ -C₄ alkanoylamino, aphenylsulfonyl, naphthylsulfonyl, phenoxy or phenylcarbonyl radical,each unsubstituted or substituted by C₁ -C₄ alkyl or halogen, R₂ ishydrogen, halogen, C₁ -C₄ alkyl, tri-fluoromethyl, a phenoxy orphenoxysulfonyl radical, each unsubstituted or substituted by C₁ -C₄-alkyl or halogen, or is ##STR7## R₃ is C₁ -C₄ alkyl or phenyl, R₄ ishydrogen or C₁ -C₈ -alkyl, and R₇ and R₈ are each independently hydrogenC₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl, C₅ -C₇ cycloalkyl, phenyl or phenylwhich is substituted by halogen, trifluoromethyl or C₁ -C₄ -alkyl.

Particularly preferred monoazo dyes are those of the formula ##STR8##wherein R₁, R₂, R₃ and R₄ are as defined for formula (1).

More particularly preferred monoazo dyes are those of the formula (2),wherein R₁ is hydrogen, methyl, chlorine, methoxy, ethoxy,o-methylphenoxy, phenoxy, acetylamino, phenylsulfonyl,p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl,p-methylbenzoyl or p-chlorobenzoyl, R₂ is hydrogen, chlorine, methyl,trifluoromethyl, o-methylphenoxy, o-chlorophenoxy,o-chlorophenoxysulfonyl, --SO₂ NH₂, N--C₁ -C₂ alkylaminosulfonyl,N,N-dimethylaminosulfonyl. N-methyl-N-β-hydroxyethylaminosulfonyl,N-methyl-n-cyclohexylaminosulfonyl, N-phenylaminosulfonyl,N-o-methylphenylaminosulfonyl, N-o-chlorophenylaminosulfonyl,N-m-trifluoromethylphenylaminosulfonyl, N-ethyl-N-phenylaminosulfonyl,--CONH₂ or --CON(CH₃)₂, R₃ is methyl or phenyl, and R₄ is hydrogen,methyl, ethyl or octyl.

Further preferred monoazo dyes are those of the formula ##STR9## whereinR₁, R₂ and R₄ are as defined for formula (1), in particular the monoazodyes of the formula (3), wherein R₁ is hydrogen, methyl, chlorine,methoxy, phenoxy, acetylamino, phenylsulfonyl, naphthylsulfonyl,p-methylphenylsulfonyl or p-chlorophenylsulfonyl, R₂ is hydrogen,chlorine, trifluoromethyl, --SO₂ NH₂,N-methyl-N-cyclohexylaminosulfonyl, phenylaminosulfonyl orN-ethyl-N-phenylaminosulfonyl, and R₄ is hydrogen or methyl.

Preferred monoazo dyes are also those of the formula ##STR10## whereinR₂, R₃ and R₄ are as defined for formula (2) and R₉ is a phenyl radicalwhich is unsubstituted or substituted by C₁ -C₄ alkyl and halogen, ornaphthyl.

In the monoazo dyes of the formula (4), the symbols have the followingpreferred meanings: R₂ is hydrogen, R₃ is phenyl, R₄ is hydrogen and R₉is phenyl.

A valuable representative is the monoazo dye of the formula ##STR11##

The present invention also relates to a process for the preparation ofthe monoazo dyes of the formula (1), which comprises diazotising a diazocomponent of the formula ##STR12## and coupling the diazonium compoundto a coupling component of the formula ##STR13## wherein R₁, R₂, R₃ andR₄ in formulae (6) and (7) are as defined for formula (1).

The diazotisation of the diazo component of the formula (6) is normallycarried out by treatment with nitrous acid in an aqueous solution ofmineral acid at low temperature, and the coupling to the couplingcomponent of the formula (7) is carried out in the acid, neutral oralkaline pH range.

It is preferred to diazotise diazo components of the formula (6),wherein R₁ is hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, C₂ -C₄alkanoyl-amino, a phenylsulfonyl, naphthylsulfonyl, phenoxy orphenylcarbonyl radical, each unsubstituted or substituted by C₁ -C₄alkyl or halogen, R₂ is hydrogen, halogen, C₁ -C₄ alkyl,trifluoromethyl, a phenoxy or phenoxysulfonyl radical, eachunsubstituted or substituted by C₁ -C₄ alkyl or halogen, or is ##STR14##and R₇ and R₈ are each independently hydrogen, C₁ -C₄ alkyl, C₁ -C₄hydroxyalkyl, C₅ -C₇ cycloalkyl, phenyl or phenyl which is substitutedby halogen, trifluoromethyl or C₁ -C₄ alkyl, and to couple the diazoniumcompound to a coupling component of the formula (7), wherein R₃ is C₁-C₄ alkyl or phenyl and R₄ is hydrogen or C₁ -C₈ alkyl. It is preferredto use a coupling component of the formula ##STR15## wherein R₃ and R₄have the above meanings.

A preferred embodiment of the process comprises diazotising a diazocomponent of the formula (6), wherein R₁ is hydrogen, methyl, chlorine,methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsulfonyl,p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl,p-methylbenzoyl or p-chlorobenzoyl; R₂ is hydrogen, chlorine, methyl,trifluoromethyl, o-methylphenoxy, o-chlorophenoxy,o-chlorophenoxysulfonyl, --SO₂ NH₂, N--C₁ -C₂ alkylaminosulfonyl,N,N-dimethylaminosulfonyl. N-methyl-N-β-hydroxyethylaminosulfonyl,N-methyl-N-cyclohexylaminosulfonyl, N-phenylaminosulfonyl,N-o-methylphenylaminosulfonyl, N-o-chlorophenylaminosulfonyl,N-m-trifluoromethylphenylaminosulfonyl, N-ethyl-N-phenylaminosulfonyl,--CONH₂ or --CON(CH₃)₂, and coupling the diazonium compound to acoupling component of the formula (8), wherein R₃ is methyl or phenyland R₄ is hydrogen, methyl, ethyl or octyl.

Another preferred embodiment of the process comprises diazotising adiazo component of the formula (6), wherein R₁ is hydrogen, methyl,chlorine, methoxy, phenoxy, acetylamino, phenylsulfonyl,naphthylsulfonyl, p-methylphenylsulfonyl or p-chlorophenylsulfonyl, R₂is hydrogen, chlorine, trifluoromethyl, --SO₂ NH₂,N-methyl-N-cyclohexylaminosulfonyl, phenylaminosulfonyl orN-ethyl-N-phenylaminosulfonyl, and coupling the diazonium compound to acoupling component of the formula (9), wherein R₄ is hydrogen or methyl.

Yet another preferred embodiment of the process comprises diazotising adiazo component of the formula (10) ##STR16## wherein R₂ is as definedfor formula (2) and R₉ is phenyl or phenyl which is substituted by C₁-C₄ alkyl and halogen, or naphthyl, and coupling the diazonium compoundto a coupling component of the formula (8).

It is preferred to use a diazo component of the formula (10), wherein R₂is hydrogen and R₉ is phenyl, and a coupling component of the formula(8), wherein R₃ is phenyl and R₄ is hydrogen.

The particularly valuable monazo dye of the formula (5) is prepared bydiazotising 2-amino-1,1'-diphenylsulfone and coupling the intermediateto 2-phenylindole-5-sulfonic acid.

The diazo components of the formula (6) are known and are prepared bymethods which are known per se.

Representative examples of the wide range of possible diazo componentsare: 2-amino-1,1'-diphenylsulfone,2-amino-4-chloro-1-phenyl-2'-naphthylsulfone,2-amino-4'-methyl-1,1'-diphenylsulfone,2-amino-4'-chloro-1,1'-diphenylsulfone,2-amino-1-phenyl-2'-naphthylsulfone,4-amino-4'-methyl-1,1'-diphenylsulfone,4-amino-4'-chloro-1,1'-diphenylsulfone, 4-amino-1,1'-diphenylsulfone,4-amino-1-phenyl-2'-naphthylsulfone,2-amino-4,4'-dimethyl-1,1'-diphenylsulfone,2-amino-4-methyl-1,1'-diphenylsulfone,2-amino-4-methyl-4'-chloro-1,1'-diphenylsulfone,2-amino-4,4'-dichloro-1,1'-diphenylsulfone,2-amino-4-chloro-4'-methyl-1,1'-diphenylsulfone,2-amino-4-trifluoromethyl-1,1'-diphenylsulfone,2-amino-4-trifluoromethyl-4'-methyl-1,1'-diphenylsulfone,2-amino-4'-chloro-1,1'-diphenylsulfone-4-sulfamide,2-amino-1,1'-diphenylsulfone-4-sulfonamide,2-amino-4'-methyl-1,1'-diphenylsulfone-4-sulfamide,2-amino-4'-methyl-1,1'-diphenylsulfone-4-N-methylsulfamide, 2-amino-4'-methyl-1,1'-diphenylsulfone-4-N,N-dimethylsulfamide,2-amino-4'-methyl-1,1'-diphenylsulfone-4-carboxamide,2-amino-4'-chloro-1,1'-diphenylsulfone-4-carboxamide,2-amino-4'-methyl-1,1'-diphenylsulfone-4-N,N-dimethylcarboxamide,2-amino-4'-chloro-1,1'-diphenylsulfone-4-N,N-dimethylcarboxamide,aniline-4-sulfamide, aniline-4-N-methylsulfamide,anilin-4-N-ethylsulfamide, aniline-2-N-methyl-N-β-hydroxyethylsulfamide,aniline-4-N-methyl-N-β-hydroxyethylsulfamide,aniline-4-N,N-dimethylsulfamide, aniline-4-N-phenylsulfamide,2-chloro-5-(4'-methylphenylcarbonyl)aniline,2-amino-1-phenyl-2'-naphthylsulfone-4-sulfamide,aniline-2-N-ethyl-N-phenylsulfamide,2-chloro-5(4'-chlorophenylcarbonyl)aniline,anilin-4-N(2'-methylphenyl)sulfamide,anilin-4-N(2'-chlorophenyl)sulfamide,anilin-4-N-(3'-trifluoromethylphenyl)sulfamide,anilin-2-N-methyl-N-cyclohexylsulfamide,4-methylaniline-3-N-phenylsulfamide,4-methylaniline-3-N-ethyl-N-phenylsulfamide,2-trifluoromethyl-4-acetylaminoaniline, 2-chloroaniline,2-methoxy-5-chloroaniline, aniline, 2-ethoxyaniline,2-(2'-chlorophenoxy)-5-chloroaniline,anilin-3-N-ethyl-N-phenylsulfamide, 2,4-di(o-methylphenoxy)aniline,2-phenoxyaniline-5-N-ethyl-N-phenylsulfamide,2-(2'-methylphenoxy)aniline, 2-methoxyaniline-5-sulfamide,2-phenoxyaniline, 2-phenoxy-5-chloroaniline, 2,3- or 3,4- or 2,4- or2,5- or 3,5- or 2,6-dichloroaniline,2-(2'-chlorophenoxysulfonyl)-5-methylaniline.

Representative examples of the large number of possible couplingcomponents are: 2-phenylindole-5-, -6- or -7-sulfonic acid,2-methylindole-5-, -6- or -7-sulfonic acid,1-octyl-2-methylindole-5-sulfonic acid, 1-methyl-2-phenylindole-5-, -6-or -7-sulfonic acid, 1-ethyl-2-methylindole-5-, -6- or -7-sulfonic acid,1-octyl-2-methylindole-6- or -7-sulfonic acid, 2-p-sulfophenylindole,2-p-sulfophenyl-1-methylindole, 2-o-sulfophenylindole and2-o-sulfophenyl-1-methylindole.

The 2-methyl- or 2-phenylindolesulfonic acids employed as couplingcomponents which contain the sulfo group in the benzene ring of theindole are obtained e.g. by reacting phenylhydrazines with ketones byFischer's indole synthesis (q.v. U.S. Pat. No. 1 866 956), or bysulfonating unsubstituted or substituted indoles in accordance withGerman patent No. 137 117. In this last mentioned process it isestablished that the sulfo group is introduced in the 5-position of theindole at least in the case of 2-phenylindole and2-methyl-N-octylindole.

The 2-sulfophenylindoles used as coupling components which can besubstituted in the 1-position by alkyl are obtained e.g. by reactingphenylhydrazines with corresponding ketones by Fischer's indolesynthesis (q.v. U.S. Pat. No. 1 866 956).

The dyes of the formula (1) are suitable for dyeing and printingmaterials which contain amide groups, for example textile fibers,textile filaments and textile fabrics made from wool, silk andpolyurethane fibers, and in particular for dyeing and printing syntheticpolyamide, using conventional dyeing methods. The dyes of formula (1)are distinguished by brilliance and tinctorial strength, good exhaustproperties and build-up, resistance to formaldehyde and by good generalfastness properties such as lightfastness, rub-fastness to acid andalkali, wetfastness, in particular fastness to washing, water, hot waterand perspiration, and they affor level dyeings.

It is to be singled out for special mention that the dyes of formula (1)combine readily with other acid dyes and are particularly suitable fordyeing or printing by the trichromatic method.

Particular attention is drawn to the fact that the dyes of formula (1)produce dyeings which have very good constancy of shade even whensubjected to the increases in temperature occurring e.g. in drying,thermofixing, steaming and ironing.

The dyes of the formula (1) are obtained either in the form of theirfree sulfonic acid or of salts thereof. Examples of suitable salts arethe alkali metal salts, alkaline earth metal salts or ammonium salts, orthe salts of an organic amine. Typical examples are the sodium, lithium,potassium or ammonium salts or the salt of triethanolamine.

The invention is illustrated by the following Examples, in which partsare by weight. The relationship between parts by weight and parts byvolume is the same as that between the gram and the cubic centimeter.

EXAMPLE 1 ##STR17##

4.66 g of 2-aminodiphenylsulfone are diazotised in 20 ml of 80% aceticacid and 5 ml of concentrated hydrochloric acid at 5° to 7° C. with 5 mlof 4N sodium nitrite. After a time the diazo solution is diluted with 50ml of ice-water and clarified by filtration.

5.46 g of 2-phenylindole-5-sulfonic acid are stirred in 50 ml of waterat room temperature and the above diazo solution is then added dropwise.When the coupling is complete, the dye is isolated by filtration, washedwith water and dried in vacuo at 60°-70° C., affording 8.7 g of dyewhich dissolves very readily in water after addition of 0.9 g of sodiumcarbonate. Brilliant yellowish orange shades of excellent lightfastnessand resistance to formaldehyde and acid are obtained when polyamidematerial is dyed from a weakly acid bath.

EXAMPLE 2 ##STR18##

4.76 g of 4-chloro-2-aminophenyl-2-naphthylsulfone are diazotised in 20ml of sulfolane with 2.5 ml of about 40% nitrosylsulfuric acid. Thediazo solution is diluted with 75 ml of water and clarified byfiltration.

3.17 g of 2-methylindole-5-sulfonic acid are dissolved in 50 ml of waterat room temperature and then the above prepared diazo solution is addeddropwise. After a time the dye is isolated by filtration and washed withwater. The moist filter cake is dissolved in water with sodium hydroxidesolution at pH 7 and the dye is salted out by adding a dilute solutionof sodium chloride. The precipitate is isolated by filtration, washedwith sodium carbonate and dried in vacuo at 60°-70° C., affording 6.5 gof a dye which dyes polyamide material from a weakly acid bath inbrilliant reddish yellow shades of good general fastness properties.

EXAMPLE 3 ##STR19##

4.02 g of aniline-2-N-methyl-N-cyclohexylsulfamide are diazotised in 20ml of sulfolane with 2.5 ml of nitrosylsulfuric acid (about 40%) and thediazo solution is then diluted with 40 ml of water. 4.85 g of2-methyl-N-octylindole-5-sulfonic acid are dissolved in 50 ml of waterat room temperature and the above prepared diazo solution is then addeddropwise to the solution of the coupling component. Upon completion ofthe coupling, the completely precipitated product is isolated byfiltration and washed with water. The filter residue is suspended inwater and the pH is adjusted to 12 with sodium hydroxide solution. Theproduct is isolated by filtration and the filter cake is dried in vacuoat 60°-70° C., affording 5.5 g of a dye which dyes polyamide material inorange shades from a weakly acid bath.

EXAMPLE 4 ##STR20##

2.7 g of the dye of Example 2, 2.12 g of sodium carbonate and 12 ml ofdimethylmethanephosphonate are heated to 120°-130° C. After 3 hours, 60ml of water and 1.2 g of sodium chloride are added and the mixture isstirred at room temperature. The precipitate is isolated by filtration,washed and dried, affording 1.9 g of alkylated dye.

Following the procedures described in Examples 1 to 4, but using thediazo components and coupling components listed in the following Table,there are also obtained water-soluble dyes which dye polyamide in theindicated shade with good fastness properties.

                                      TABLE                                       __________________________________________________________________________                                                          Shade on                Example                                                                            Diazo component            Coupling component    polyamide               __________________________________________________________________________     1                                                                                  ##STR21##                                                                                                ##STR22##            yellowish orange         2   "                                                                                                         ##STR23##            "                        3                                                                                  ##STR24##                                                                                                ##STR25##            yellowish orange         4                                                                                  ##STR26##                                                                                                ##STR27##            yellowish orange         5                                                                                  ##STR28##                                                                                                ##STR29##            yellowish orange         6                                                                                  ##STR30##                                                                                                ##STR31##            yellowish orange         7                                                                                  ##STR32##                                                                                                ##STR33##            yellowish orange         8                                                                                  ##STR34##                                                                                                ##STR35##            "                        9                                                                                  ##STR36##                                                                                                ##STR37##            yellowish orange        10                                                                                  ##STR38##                                                                                                ##STR39##            "                       11                                                                                  ##STR40##                                                                                                ##STR41##            yellowish orange        12   "                                                                                                         ##STR42##            yellow                  13                                                                                  ##STR43##                                                                                                ##STR44##            yellow                  14   "                                                                                                         ##STR45##            "                       15                                                                                  ##STR46##                                                                                                ##STR47##            yellow                  16   "                                                                                                         ##STR48##            "                       17                                                                                  ##STR49##                                                                                                ##STR50##            yellow                  18   "                                                                                                         ##STR51##            orange                  19                                                                                  ##STR52##                                                                                                ##STR53##            orange                  20   "                                                                                                         ##STR54##            "                       21                                                                                  ##STR55##                                                                                                ##STR56##            yellowish orange        22   "                                                                                                         ##STR57##            "                       23                                                                                  ##STR58##                                                                                                ##STR59##            yellowish orange        24   "                                                                                                         ##STR60##            reddish yellow          25                                                                                  ##STR61##                                                                                                ##STR62##            yellow                  26   "                                                                                                         ##STR63##            "                       27                                                                                  ##STR64##                                                                                                ##STR65##            yellow                  28   "                                                                                                         ##STR66##            "                       29                                                                                  ##STR67##                                                                                                ##STR68##            yellowish orange        30                                                                                  ##STR69##                 "                     "                       31                                                                                  ##STR70##                 "                     "                       32                                                                                  ##STR71##                                                                                                ##STR72##            yellowish orange        33   "                                                                                                         ##STR73##            "                       34                                                                                  ##STR74##                                                                                                ##STR75##            yellowish orange        35   "                                                                                                         ##STR76##            yellow                  36                                                                                  ##STR77##                                                                                                ##STR78##            yellow                  37   "                                                                                                         ##STR79##            "                       38                                                                                  ##STR80##                                                                                                ##STR81##            yellow                  39   "                                                                                                         ##STR82##            "                       40                                                                                  ##STR83##                                                                                                ##STR84##            yellow                  41                                                                                  ##STR85##                                                                                                ##STR86##            "                       42                                                                                  ##STR87##                                                                                                ##STR88##            yellow                  43                                                                                  ##STR89##                                                                                                ##STR90##            yellowish orange        44                                                                                  ##STR91##                                                                                                ##STR92##            yellowish orange        45   "                                                                                                         ##STR93##            "                       46                                                                                  ##STR94##                                                                                                ##STR95##            yellowish orange        47   "                                                                                                         ##STR96##            "                       __________________________________________________________________________

    __________________________________________________________________________    48                                                                                  ##STR97##                                                                                                ##STR98##            yellowish orange        49   "                                                                                                         ##STR99##            yellow                  50                                                                                  ##STR100##                                                                                               ##STR101##           yellow                  51   "                                                                                                         ##STR102##           "                       52                                                                                  ##STR103##                                                                                               ##STR104##           yellow                  53   "                                                                                                         ##STR105##           "                       54                                                                                  ##STR106##                                                                                               ##STR107##           yellow                  55                                                                                  ##STR108##                                                                                               ##STR109##           "                       56                                                                                  ##STR110##                                                                                               ##STR111##           yellow                  57   "                                                                                                         ##STR112##           reddish yellow          58                                                                                  ##STR113##                                                                                               ##STR114##           yellowish orange        59   "                                                                                                         ##STR115##           "                       60                                                                                  ##STR116##                                                                                               ##STR117##           yellowish orange        61   "                                                                                                         ##STR118##           "                       62                                                                                  ##STR119##                                                                                               ##STR120##           yellowish orange        63   "                                                                                                         ##STR121##           "                       64                                                                                  ##STR122##                                                                                               ##STR123##           yellow                  65   "                                                                                                         ##STR124##           "                       66                                                                                  ##STR125##                                                                                               ##STR126##           yellow                  67   "                                                                                                         ##STR127##           "                       68                                                                                  ##STR128##                                                                                               ##STR129##           yellow                  69   "                                                                                                         ##STR130##           "                       70                                                                                  ##STR131##                                                                                               ##STR132##           yellowish orange        71   "                                                                                                         ##STR133##           "                       72                                                                                  ##STR134##                                                                                               ##STR135##           yellow                  73   "                                                                                                         ##STR136##           "                       74                                                                                  ##STR137##                                                                                               ##STR138##           yellowish orange        75   "                                                                                                         ##STR139##           "                       76                                                                                  ##STR140##                                                                                               ##STR141##           yellowish orange        77   "                                                                                                         ##STR142##           "                       78                                                                                  ##STR143##                                                                                               ##STR144##           yellowish orange        79   "                                                                                                         ##STR145##           "                       80                                                                                  ##STR146##                                                                                               ##STR147##           yellow                  81   "                                                                                                         ##STR148##           "                       82                                                                                  ##STR149##                                                                                               ##STR150##           yellow                  83   "                                                                                                         ##STR151##           "                       84                                                                                  ##STR152##                                                                                               ##STR153##           yellow                  85   "                                                                                                         ##STR154##           "                       86                                                                                  ##STR155##                                                                                               ##STR156##           yellowish orange        87   "                                                                                                         ##STR157##           "                       88                                                                                  ##STR158##                                                                                               ##STR159##           yellow                  89   "                                                                                                         ##STR160##           "                       90                                                                                  ##STR161##                                                                                               ##STR162##           yellowish orange        91   "                                                                                                         ##STR163##           "                       92                                                                                  ##STR164##                                                                                               ##STR165##           yellow                  93   "                                                                                                         ##STR166##           "                       94                                                                                  ##STR167##                                                                                               ##STR168##           yellow                  95   "                                                                                                         ##STR169##           "                       96                                                                                  ##STR170##                                                                                               ##STR171##           yellow                  97   "                                                                                                         ##STR172##           yellowish               __________________________________________________________________________                                                          orange              

    __________________________________________________________________________     98                                                                                 ##STR173##                                                                                               ##STR174##           yellowish orange         99                                                                                 ##STR175##                "                     "                       100                                                                                 ##STR176##                                                                                               ##STR177##           yellowish orange        101                                                                                 ##STR178##                                                                                               ##STR179##           reddish yellow          102                                                                                 ##STR180##                                                                                               ##STR181##           reddish yellow          103                                                                                 ##STR182##                                                                                               ##STR183##           "                       104                                                                                 ##STR184##                                                                                               ##STR185##           reddish yellow          105  "                                                                                                         ##STR186##           yellowish orange        106                                                                                 ##STR187##                                                                                               ##STR188##           orange                  107                                                                                 ##STR189##                "                     "                       108                                                                                 ##STR190##                                                                                               ##STR191##           orange                  109                                                                                 ##STR192##                "                     "                       110                                                                                 ##STR193##                                                                                               ##STR194##           orange                  111                                                                                 ##STR195##                "                     "                       112                                                                                 ##STR196##                                                                                               ##STR197##           orange                  113                                                                                 ##STR198##                "                     "                       114                                                                                 ##STR199##                                                                                               ##STR200##           yellowish orange        115                                                                                 ##STR201##                                                                                               ##STR202##           orange                  116                                                                                 ##STR203##                                                                                               ##STR204##           yellow                  117                                                                                 ##STR205##                "                     "                       118                                                                                 ##STR206##                                                                                               ##STR207##           yellow                  119                                                                                 ##STR208##                "                     "                       120                                                                                 ##STR209##                                                                                               ##STR210##           yellow                  121                                                                                 ##STR211##                "                     "                       122                                                                                 ##STR212##                                                                                               ##STR213##           yellow                  123  "                                                                                                         ##STR214##           "                       124                                                                                 ##STR215##                                                                                               ##STR216##           yellow                  125                                                                                 ##STR217##                                                                                               ##STR218##           reddish yellow          126                                                                                 ##STR219##                                                                                               ##STR220##           reddish yellow          127                                                                                 ##STR221##                "                     "                       128                                                                                 ##STR222##                                                                                               ##STR223##           reddish yellow          129                                                                                 ##STR224##                "                     yellowish orange        130                                                                                 ##STR225##                                                                                               ##STR226##           reddish yellow          131                                                                                 ##STR227##                "                     yellowish orange        132                                                                                 ##STR228##                                                                                               ##STR229##           yellow                  133                                                                                 ##STR230##                "                     yellowish orange        134                                                                                 ##STR231##                                                                                               ##STR232##           yellowish orange        135                                                                                 ##STR233##                                                                                               ##STR234##           yellow                  136                                                                                 ##STR235##                                                                                               ##STR236##           reddish yellow          137                                                                                 ##STR237##                                                                                               ##STR238##           yellow                  138                                                                                 ##STR239##                                                                                               ##STR240##           reddish yellow          139                                                                                 ##STR241##                                                                                               ##STR242##           reddish yellow          140                                                                                 ##STR243##                "                     yellow                  __________________________________________________________________________

    __________________________________________________________________________    141                                                                                 ##STR244##                                                                                               ##STR245##           reddish yellow          142                                                                                 ##STR246##                                                                                               ##STR247##           reddish yellow          143                                                                                 ##STR248##                                                                                               ##STR249##           reddish yellow          144                                                                                 ##STR250##                                                                                               ##STR251##           reddish yellow          145                                                                                 ##STR252##                                                                                               ##STR253##           yellowish orange        146                                                                                 ##STR254##                "                     "                       147                                                                                 ##STR255##                                                                                               ##STR256##           yellowish orange        148                                                                                 ##STR257##                "                     "                       149                                                                                 ##STR258##                                                                                               ##STR259##           yellowish orange        150                                                                                 ##STR260##                "                     "                       151                                                                                 ##STR261##                                                                                               ##STR262##           yellowish orange        152                                                                                 ##STR263##                "                     "                       153                                                                                 ##STR264##                                                                                               ##STR265##           yellowish orange        154                                                                                 ##STR266##                "                     "                       155                                                                                 ##STR267##                                                                                               ##STR268##           yellowish orange        156                                                                                 ##STR269##                "                     "                       157                                                                                 ##STR270##                                                                                               ##STR271##           yellowish orange        158                                                                                 ##STR272##                "                     "                       159                                                                                 ##STR273##                                                                                               ##STR274##           yellowish orange        160                                                                                 ##STR275##                "                     reddish yellow          161                                                                                 ##STR276##                                                                                               ##STR277##           yellowish orange        162                                                                                 ##STR278##                "                     "                       163                                                                                 ##STR279##                                                                                               ##STR280##           yellowish orange        164                                                                                 ##STR281##                "                     "                       165                                                                                 ##STR282##                                                                                               ##STR283##           yellowish orange        166                                                                                 ##STR284##                                                                                               ##STR285##           yellowish orange        167                                                                                 ##STR286##                "                     "                       168                                                                                 ##STR287##                                                                                               ##STR288##           yellowish orange        169                                                                                 ##STR289##                "                     reddish yellow          170                                                                                 ##STR290##                                                                                               ##STR291##           yellowish orange        171                                                                                 ##STR292##                "                     reddish yellow          172                                                                                 ##STR293##                                                                                               ##STR294##           yellowish orange        173                                                                                 ##STR295##                "                     "                       174                                                                                 ##STR296##                                                                                               ##STR297##           yellowish orange        175                                                                                 ##STR298##                "                     "                       176                                                                                 ##STR299##                                                                                               ##STR300##           yellowish orange        177                                                                                 ##STR301##                "                     reddish yellow          178                                                                                 ##STR302##                                                                                               ##STR303##           yellowish orange        179                                                                                 ##STR304##                                                                                               ##STR305##           reddish yellow          180                                                                                 ##STR306##                                                                                               ##STR307##           yellowish orange        181                                                                                 ##STR308##                "                     "                       182                                                                                 ##STR309##                                                                                               ##STR310##           yellowish orange        183                                                                                 ##STR311##                                                                                               ##STR312##           "                       184                                                                                 ##STR313##                                                                                               ##STR314##           yellowish orange        185                                                                                 ##STR315##                "                     "                       186                                                                                 ##STR316##                                                                                               ##STR317##           reddish                 __________________________________________________________________________                                                          yellow              

DYEING PROCEDURE I

10 parts of Helanca® tricot are dyed in 500 parts of an aqueous liquorwhich contains 2 g/l of ammonium acetate and is adjusted with aceticacid to pH 5. The concentration of dye of Example 1 is 0.7%, based onthe weight of the fabric. The dyeing time at 98° C. is 30 to 90 minutes.The dyed tricot fabric is then removed from the bath and washed anddried in the conventional manner.

The tricot fabric is dyed in a pure yellowish orange shade of goodgeneral fastness properties.

DYEING PROCEDURE II

10 parts of Helanca® tricot are dyed in 500 parts of an aqueous liquorwhich contains 1 g/l of monosodium phosphate and is adjusted withdisodium phosphate to pH 6. The concentration of dye of Example 74 is1%, based on the weight of the fabric. The dyeing time at 98° C. is 30to 90 minutes. The dyed tricot fabric is then removed from the bath andwashed and dried in the conventional manner. The tricot is dyed in apure yellowish orange shade of good general fastness properties.

DYEING PROCEDURE III

10 parts of woolen piece goods are dyed in an aqueous liquor containing0.8% of the dye of Example 1, 5% of calcined Glauber's salt and 4% of96% sulfuric acid, in each case based on the weight of the fabric. Thedyeing time at 98° C. is 30 to 60 minutes. The dyed wool is washed anddried in the conventional manner and has very good general fastnessproperties.

DYEING PROCEDURE IV

10 parts of a wool/polyamide blend (50:50) are dyed in an aqueous liquorwhich contains 0.8% of the dye of Example 1, 5% of calcined Glauber'ssalt, 1% of a levelling agent, 2% of 80% acetic acid and 2% of aretarding and levelling auxiliary, in each case based on the weight ofthe fabric. The dyeing time is 30 to 60 minutes at 98° C. The fabric,which is washed and dried in the conventional manner, is dyedtone-in-tone.

DYEING PROCEDURE V

10 parts of Helanca® tricot fabric are dyed in 500 parts of an aqueousliquor which contains 2 g/l of ammonium acetate and is adjusted withacetic acid to pH 5. The dye liquor contains 0.75 g of the yellow dye ofthe formula ##STR318## 0.8% of the red dye of the formula ##STR319## and0.49% of the blue dye of the formula ##STR320## the amounts being basedin each case on the weight of the fabric. The dyeing time is 30 to 60minutes at 98° C. The dyed tricot fabric is washed and dried in theconventional manner. A completely level reddish brown dyeing with notrace of material-induced barriness is obtained.

DYEING PROCEDURE VI

500 m² of a polyamide 66 cut-pile carpet (brushed goods backed withpolypropylene tape fabric) having a weight of 535 g/m² are continuouslyprewetted in a liquor which contains 1 g/liter of the polyadduct of 1mole of nonylphenol and 9 moles of ethylene oxide, and then expressed toa pick-up of 40% by weight.

A dye foam having a blow ratio of 1:10 is prepared in a mixer from anaqueous liquor of the following composition: 0.45 g/l of the red dye ofthe formula ##STR321## 0.9 g/l of the yellow dye of the formula##STR322## 0.3 g/l of the blue dye mixture which contains the dyes ofthe formulae ##STR323## in the ratio 1:1, 2.5 g/l of a foam stabilisermixture consisting of coconut fatty acid diethanolamide/nonylphenolpolyglycol(11) ether and sodium lauryl triglycol ether sulfate,

0.6 g/l of the oxyalkylene-siloxane copolymer of the formula ##STR324##1 g/l of sodium acetate, and acetic acid for adjusting the pH value ofthe liquor to 6.

This foam is then applied from a container, equipped with a knife foradjusting the desired thickness of the foam, via an applicator rollusing a carriage to the pile side of the carpet which passes through thedyeing unit at a rate of 9 m/minute. The height of the foam is 8 mm. Thefoam add-on is 135%.

A vaccum (˜0.1 bar) is then applied to the back of the carpet in orderto effect partial penetration of the layer of foam into the carpet,whereby the height of the foam is somewhat reduced. The carpet thenpasses over a conveyor roll into a steamer (102° C., saturated steam),where the foam rises slightly and is then collapsed. The carpet issubsequently sprayed with water of 80° C., then centrifuged, and driedat 100° C.-130° C. in a cylindrical sieve drier.

The carpet fabric is dyed in a level beige shape with excellentpenetration of the dye. The foam dyeing has a positive influence on thesoftness and bulk of the fabric.

DYEING PROCEDURE VII (CARPET PRINTING)

A polyamide 6 cut-pile fitted carpet having a weight of 350 to 400 g/m²is impregnated on a padder with a padding liquor consisting of 988 partsof water, 10 parts of 36° Be sodium hydroxide solution and 2 parts ofwetting agent, and squeezed out to a pick-up of 80%.

A dye paste of the following composition is sprayed in the form of apattern, by means of a nozzle, onto the pretreated carpet:

942 parts of water,

50 parts of a thickener,

3 parts of an antifoam,

5 parts of the red dye of the formula ##STR325## 1.5 parts of the yellowdye of the formula ##STR326## 1 part of the blue dye mixture whichcontains the dyes of the formulae ##STR327## in the rato 1:1.

The thickener used has the following composition: 240 parts of whitespirit, 50 parts of a water-in-oil emulsifier, 20 parts of anoil-in-water emulsifier, 20 parts of an antifoam, 50 parts of acrosslinked carboxyvinyl polymer having a molecular weight of approx.4.000.000, 70 parts of a linear carboxyvinyl polymer having a molecularweight of approx. 1.000.000 and 550 parts of water, the pH having beenadjusted to a value of 4.5 with acetic acid.

The material which has been sprayed with the dye paste is then treatedwith saturated steam at 101° C. for 5 minutes in order to fix the dyes,then rinsed, neutralised, rinsed again and dried.

A claret shade pattern with very sharp contours is obtained on thecut-pile fitted carpet. Dye penetration is very good and there isabsolutely no frosting.

DYEING PROCEDURE VIII (CONTINUOUS CARPET DYEING)

2.7 parts of the yellow dye of the formula ##STR328## 1.2 parts of thered dye of the formula ##STR329## and 1.3 parts of the blue dye of theformula ##STR330## are dissolved in 100 parts of water by brief boiling.This solution is then added to a solution containing 3 parts of athickener based on locust beam gum, 5.0 parts of a coacervate-formingpadding assistant based on a condensation product of a higher-molecularfatty acid with an oxyalkylamine, 2.0 parts of crystalline monosodiumphosphate and 1.0 part of crystalline disodium phosphate in 500 parts ofcold water. The mixture is then bulked to 1000 parts with cold water.300% (based on the weight of carpet) of this liquor, which has a pHvalue of 5.5 to 6.5, are then applied to a polyamide tufted undyedcarpet, at a carpet speed of 8 meters per minute. The impregnated carpetis passed into a festoon steamer, where it is treated for 10 minuteswith saturated steam at 98° to 100° C. The carpet is then washed in anopen width washing machine. It is dyed in a neutral brown shade.

What is claimed is:
 1. A monoazo dye of the formula ##STR331## whereinR₁₀ is hydrogen and R₁₁ is phenoxy or naphthoxy each unsubstituted orsubstituted by C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen, C₁₋₆ -alkanoylaminoor hydroxyl, or ##STR332## and R₁₄ and R₁₅ are each independently C₁₋₄-alkyl, C₁₋₄ -hydroxyalkyl or C₅₋₇ -cycloalkyl; or R₁₀ is C₁₋₄ -alkyland R₁₁ is phenoxy or naphthoxy each unsubstituted or substituted byC₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen, C₁₋₆ -alkanoylamino or hydroxyl; orR₁₀ is C₁₋₄ -alkoxy and R₁₁ is hydrogen, halogen, C₁₋₁₂ -alkyl, phenoxy,naphthoxy, phenoxysulfonyl, naphthoxysulfonyl each unsaturated orsubstituted by C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen, C₁₋₆ -alkanoylaminoor hydroxyl, or ##STR333## and R₁₆ and R₁₇ are each independently C₁₋₁₂-alkyl unsubstituted or substituted by halogen, hydroxyl, cyano, C₁₋₄-alkoxy, C₁₋₆ -alkanoyl or benzoyl, cycloalkyl containing 5- to7-membered ring unsubstituted or substituted by C₁₋₄ -alkyl; or R₁₀ ishalogen and R₁₁ is phenoxy or naphthoxy each unsubstituted orsubstituted by C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen, C₁₋₆ -alkanoylaminoor hydroxyl; or R₁₀ is C₂₋₄ -alkanoylamino and R₁₁ is hydrogen, halogen,C₁₋₁₂ -alkyl, phenoxy, naphthoxy, phenoxysulfonyl or naphthoxysulfonyleach unsubstituted or substituted by C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen,C₁₋₆ -alkanoylamino or hydroxyl, or ##STR334## and R₁₈ and R₁₉ are eachindependently C₁₋₁₂ -alkyl unsubstituted or substituted by halogen,hydroxyl, cyano, C₁₋₄ -alkoxy, C₁₋₆ -alkanoyl or benzoyl, cycloalkylcontaining 5- to 7-membered ring unsubstituted or substituted by C₁₋₄-alkyl; or phenyl or naphthyl each unsubstituted or substituted by C₁₋₄-alkyl, C₁₋₄ -alkoxy, halogen, trifluoromethyl, C₁₋₆ -alkanoylamino,hydroxyl or carbonyl; R₁₂ is C₁₋₁₂ -alkyl unsubstituted or substitutedby halogen, hydroxyl, cyano, C₁₋₄ -alkoxy, C₁₋₆ -alkanoyl or benzoyl orphenyl or naphthyl each unsubstituted or substituted by C₁₋₄ -alkyl,C₁₋₄ -alkoxy, halogen, trifluoromethyl, C₁₋₆ -alkanoylamino, hydroxyl,carboxyl or sulfo; and R₁₃ is hydrogen or C₁₋₁₂ -alkyl.
 2. A monoazo dyeaccording to claim 1, wherein R₁₀ is hydrogen and R₁₁ is ##STR335## R₁₄and R₁₅ are each independently C₁₋₄ alkyl, C₁₋₄ -hydroxyalkyl or C₅₋₇-cycloalkyl, or R₁₀ is C₁₋₄ -alkoxy and R₁₁ is hydrogen or halogen, orR₁₀ is halogen and R₁₁ is phenoxy or naphthoxy each unsubstituted orsubstituted by C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen, C₁₋₆ -alkanoylaminoor hydroxyl; or R₁₀ is C₂₋₄ -alkanoylamino and R₁₁ is hydrogen, halogen,or ##STR336## and R₁₈ and R₁₉ are each independently C₁₋₁₂ -alkylunsubstituted or substituted by halogen, hydroxyl, cyano, C₁₋₄ -alkoxy,C₁₋₁₆ -alkanoyl or benzoyl, cycloalkyl containing 5- to 7-membered ringunsubstituted or substituted by C₁₋₄ -alkyl; or phenyl or naphthyl eachunsubstituted or substituted by C₁₋₄ -alkyl, C₁₋₄ -alkoxy, halogen,trifluoromethyl, C₁₋₆ -alkanoylamino, hydroxyl or carbonyl; R₁₂ is C₁₋₁₂-alkyl unsubstituted or substituted by halogen, hydroxyl, cyano, C₁₋₄-alkoxy, C₁₋₆ -alkanoyl or benzoyl or phenyl or naphthyl eachunsubstituted or substituted by C₁₋₄ -alkyl C₁₋₄ -alkoxy, halogen,trifluoromethyl, C₁₋₆ -alkanoylamino, hydroxyl, carboxyl or sulfo; andR₁₃ is hydrogen or C₁₋₁₂ -alkyl.
 3. A monoazo dye according to claim 2,wherein R₁₀ is C₁₋₄ -alkoxy and R₁₁ is hydrogen or halogen.
 4. A monoazodye according to claim 2, wherein R₁₀ is halogen and R₁₁ is phenyloxy orphenyloxy which is substituted by C₁₋₄ -alkyl or halogen.
 5. A monoazodye according to claim 2, wherein R₁₀ is C₂₋₄ -alknoylamino and R₁₁ ishydrogen, halogen or a radical of the formula ##STR337## and R₁₈ and R₁₉are each independently C₁₋₄ -alkyl, C₁₋₄ -hydroxyalkyl, C₅₋₇-cycloalkyl, phenyl or phenyl substituted by halogen, trifluoromethyl orC₁₋₄ -alkyl.
 6. A monoazo dye according to claim 2, wherein R₁₂ is C₁₋₄-alkyl or phenyl and R₁₃ is hydrogen or C₁₋₈ -alkyl.
 7. A monoazo dyeaccording to claim 2, of the formula ##STR338##
 8. A monoazo dyeaccording to claim 2, of the formula ##STR339##
 9. A monoazo dye of theformula ##STR340## wherein R₁ is phenylsulfonyl, naphthylsulfonyl,p-methylphenylsulfonyl or p-chlorophenylsulfonyl, R₂ is hydrogen,chlorine, trifluoromethyl, --SO₂ NH₂,N-methyl-N-cyclohexylaminosulfonyl, phenylaminosulfonyl orN-ethyl-N-phenylaminosulfonyl, and R₄ is hydrogen or methyl.
 10. Amonoazo dye of the formula ##STR341## wherein R₂ is hydrogen, R₃ isphenyl, R₄ is hydrogen and R₉ is phenyl.
 11. The monoazo dye accordingto claim 10, of the formula ##STR342##